Resinous condensation product



- for their manufacture having marked ad-l.

Patented Apr. 12, 1932 um'rsn STA TEST-PATENT OFFICE KENNETH, H. noovnn, or DEEBFIELD, rumors, ASSIGNOB r ASSOCIATION or AMERICAN SOAP AND GLYGERINE PRODUCERS, INC., A CORPORATION OF DELAWARE BESINOUS CONDENSATION PRODIl'CT No Drawing. Application filed Kay 12,

The 'present invention. relates 'to improvements in resinous condensation products or estercomplexes derived from certain glycerol derivatives, and moreparticularly to resinous bodies of this type and to methods vantages in production and in utilization.

In accordance with the present inventionresinous ester bodies are produced which are- 1 particularly advantageous for use indus-v trially, more especially in adhesives and protective films and as components of n1 trocellulose lacquers. Theresinous bodies pro-. duced 1n accordance with this lnventlon ma vary. from soft, balsam-like resins to" bar tou h resinous materials while retaining solu ility in common organic solvents without requiring the use of modifying agents in their manufacture such as are commonly used to maintain the solubility of other types of synthetic resins. Furthermore, resinous.

bodies with very low acid numbers may be produced in accordance'withthe present invention; and their solutions have low viscosities, even without the use of modifying agents in their manufacture, and notwith standing low acidity of the resins.

In operating in accordance with the present invention to produce such resins, there are no. .well defined critical heating periods.

such as are found ordinarily in'synthesizing resinous bodles, wherein marked changes in the properties of'the compounds are proproperties of the duced in very short periods of time, with re-,

sultin insolubility in common organic compoun s and occaslonally infusibility. 4 Since such critical points in the manufacturing process are not present in operating inaccordance with thexpresent invention, this process is particularly adapted to large. I scale industrial manufacture and has the further advantage that. re reduction of product ombatch to batch is greatly facilitated.

y In accordance with the present invention, esterifiable ethers of glycerol and a cyclic compound are condensed with polybasic carboxylic acids to form resinous ester bodies. The term esterifiable ethers of glycerolin this, specification designates the mono and 1930. Serial No. 451,855.

di-ethers of glycerol, since the tii-ethers of glycerol are incapable of esterification unless hydroxyl substitutions occur in the ether radicals. In accordance with this invention, the glycerol ethers of this character are em-'' ployed; that is aromatic and heterocyclic monoand di-eth ers of glycerol wherein theglycerol residue constitutes one radical and another ether radical is an aromatic or heterocyclic residue, substituted or unsubstituted. Ordinarily it is desirable to use only a-mono-ether. of glycerol in preparing resinous bodies in accordance with this invention; but, in certain cases, as where a softer resin is desired, it may be produced by utilizing a suitable proportion of a di-ether of glcerolwith the mono-ether. Compound ethers, that is, glycerol di-ethers havin dissimilar ether radicals, one or both of wh ch are cyclic, are

included in operating in accordance with the present invention, as well as are mixtures of two or more glycerol ethers. Thus, Imay employ such ethers as the benzyl, hydroxyphenyl, carboxyphenyl, cresyl, furfuryl, chlorophenyl and naphthyl ethers of glycerol, or compound ethers thereof. I

The esterifiable glycerol ether of a cyclic body is caused to react with a olybasic carbox lic acid or. its anhydnde such as pht alic, succinic, maleic and adipic acid or the anhydrides' of one 0 them, or mixtures thereof. Ordinarily, for economic reasons,

the polybasic-acid; and the hea mg is con 'tinued until aresinous body having the desired properties with respect to acid number or hardness is secured. Resinous bodies having acid numbers of 25 or less may be pro- "duced which are soluble inthe'usllal lacquer solvents. 'On continuing the reduction of the acid numbers, say to 10 orless by continued heating, the resins remain clear, S9111-- phthalic anhydride is preferred. Molecular sulting bodies having the general properties hereinbefore set forth. The following exam ples are illustrative of the invention.

Example 1 420 parts of u-glyceryl phenyl ether (CH OHCHOH.OH OC H and 370 parts of phthalie anhydride are charged into an open reaction vessel which may be made suitably of aluminum or maybe glass lined. The charge heated to 220-225 C. during the course of 2-3 hours, such heating being accomplished by raising the temperature rapidly at first to approximately C. as for example during the first 1-1 5 hours and then gradually to 220225 C. during the last 1-1 hours of this initial heating period. During this period of heating, volatilization of the reacting constituents is prevented, at least in part, as by a reflux condenser or a vented cover.

When the reaction temperature has reached 220-225 C., heating is continued Within this range of temperatures with the vessel open until a 1-2 gram test sample of the batch dissolved in 50 cc. of a mixture of equal parts by volume ethanol and benzene,

and titrated with N/lO potassium hydroxide solution, using phenolphthalein as indicator. has an acid number of 10 or less (mgm. KOH per gm.). This time of heating at 220225 C. necessary to carry the reaction to this specific point, i. e., a resin having an acid number of 10 or less, will depend upon several factors such as the physical characteristics of the vessel and the batch size, which in turn will determine the relation of surface area of the batch exposed and heated surface to its total volume. During the early stages of the reaction the volatile products given off consist largely of water vapor, accompanied by small quantities of the reactants themselves. During the later stages of the reaction water is still givenoff but substantial quantities of phthalic anhyd ride are like- Wise volatilized. The time of heating at 220225 (l. should normally not exceed 8-10 hours in producing a resin having an acid number of 10 or less. The rate of decrease of the acidity of. the resin becomes increasingly slower as the resin approaches neutrality. 5 6 hours heating at 220225 C. should normally sullice under the same conditions to reduce the acid number to 25 or less.

Various expedieuts well known to the resin art may be en'iployed to increase the rate of reaction and/or reduction of said acid numbers. For example. the reaction may be carried out in a elosable vessel under reduced pressures during the reaction or an inert gas may be passed through the reaction mixture to hasten the removal of volatile products of the reaction. The latter expedient also has the advantage of producing resins of better color, as it provides a non-oxidizing atmosphere for the reaction.

In the. production of large batches of the resin, particularly when heated by direct flame, agitation of the reaction mixture may be employed to advantage to prevent local over-heating in the charge and to hasten the reaction.

The finished resin having an acid number of 10 or less is a hard clear resin having a brownish-red color. It is soluble in organic esters and aromatic hydrocarbons and in mixtures of esters, alcohols and hydrocarbons such as are ordinarily used in lacquer compositions. It is compatible with nitrocellulose in all proportions in the lacquers as ordinarily formulated.

If the condensation has been carried only through the shorter heating period the resin having an acid number approximating 25 will be somewhat softer and will have a lighter color but otherwise will exhibit substantially the same properties as the resin of lower acidity.

Example 2 112 parts by weight of the tetrahydrofurfuryl ether of glycerol,

C H O .H .CHOH.CH OH,

and 96 parts of phthalic anhydride are charged to a suitable container of aluminum or glass lined material. 'lhe'charge is heated in the manner set forth in Example 1 to effect the desired condensation and secure a product of the desired acid number.

The finished resin having an acid number of approximately 10 is a soft, clear resin, dark brown in color. It is soluble in acetone,. a mixture of alcohol and benzene and in mix tures of esters, alcohols and hydrocarbons such as are ordinarily used in formulating lacquers. It is compatible with nitrocellulose in such lacquers.

The following additional examples illustrate the invention further 366 parts of a-glyceryl phcnyl ether (CI-L0H.CHOHCH OC H 157 parts of mglyceryl diphenyl ether (COH OCH;.OHOHCILOC IL) and 370 parts of phthalic anhydride are condensed as in the preceding examples, yielding a resin somewhatsofter than the" resin prepared from u-glyceryl phcnyl ether and pbthalic anhydride but otherwise exhibiting similar properties.

168 parts of wglyceryl phenyl'ether and 118 parts of succinic acid are condensed in astaoae accordance with this invention,yieldin a reddishebrown resin of lighter color, so r and somewhat more elastic than the a-glyceryl phenyl ether-phthalic anhydride resin. Itis soluble in toluene and butyl acetate and in the usual lacquer solvent mixtures.

202.5 parts of usglyceryl ortho chlorov phenyl ether.-

oI-noHcHoHcmodmon andl48 parts of phthalic anhydride are condensed as hereinbefore described and yield a resin exhibiting substantially the same,

1 physical properties and the same solubilities as the or-glyceryl phenyl ether-phthalic anhydride resin. r It has been customary hitherto to use modi- 4 fying agents in synthetic resin manufacture.

These modifying agents may be employed with resins producedin accordance with the present invention. Most important among these modifying agents'are polyh dric alcohols such as .ethylene glycol an monobasie carboxylic acids such as 'oleic, linoleic, and abietic acids;.oils, drying or non-drying, such as linseed and castor oils;

and natural resins such as rosin.

Previously the use of modifying agents, other than the polyhydric'alcohols, has been largely for the modification of resins otherwise insoluble inthe ordinary organic sol-" ventsor for the reduction of the acidity 'of the resins or. the viscosity of their solutions 85 and likewise to make the resin compatible with nitrocellulose where the resin is to be I used in lacquer compositions. The resinous The use of portions of a such as glycerol in connection with the procester complexes. produced in accordance with thls invention are normally soluble in such solvents, have low acidities and viscosities, and are compatible with nitrocellulose without the use of such modifying agents in their manufacture. The use of modifying agents to produce such characteristics in. these tresins is hence unnecessary for the purposes for which they have hitherto been employed. It is to be understood, however, that the use of modifying agents in the manufacture of these resinous ester complexes may be desir able and is in many cases highly advantage-- ous in modifying the characteristics of the resinous body and mixtures thereof with nitrocellulose and other lacquer materials.

For example, by carrying out the processin the manner hereinbeforedescribed, em-

I ploying l68'parts ofa-glyceryl phenyl ether,

148 parts of phthalic anhydride and 56 parts of castor oi, the product is a soft'resin, lighter in color than the correspondin resin produced without the castor oil, but aving similar solubilities. I

"polyhydricalcohol ess of this invention for modificationof the resinous ester complexes comprising this inventlon tends to produce insolubility of the glycerol;

various expedients known to the art of resin manufacture are applicable to the present processes. For example, the condensations may be effected in an atmosphere of aninert gas; an inert gas may be blown through the resin during the condensation to hasten the removal of volatile products from the reaction mixture, or the condensations may be carried out at reduced or increased pressures. Further, the time and temperatures for effecting these reactions may vary within wide 7 limits to produce substantially the same ul-- timate resinous products. The condensation of various'glycerol ethers or the use of modifying agents may render such ,variations desirable or necessary. A

In the manufacture of synthetic resins, as hitherto conducted, the resins pass through several stages of condensation and unless modifying agents are used in their syntheses the resins may have varyingdegrees of infusibility and insolubility. This transition from a fusible soluble condition to infusibil ity and 'insolubility is generally a rapid transsition in which the properties ,of the resin change very rapidly during a short period v of time. In certain estertypes of synthetic resins complete esterification cannot be ac-.

complished gelation of the resins and rapid transition to infusibility and insolubility occurring at relatively high acidities of the resin. The use of modifying agents has therefore-been resorted to in order to elfect the esterification more completely and maintain no I solubility of the resin. Even then it is difiicult to complete the esterification and. ap-

p'roach neutrality in the resin .unless such quantities of-modifying agents are used as to adversely. affect other desirable properties.

of the resin. v

The resinous ester complexes produced in accordance with this invention are incapable of; gelation within reasonable heating periods and the properties of the resinous prodmaterially during short,

nets do 'not 0 an 0 critical periods o heating', even near the end of the condensation: which is generally; a

critical periodfor other types of resins.even- :.f;-f when modifying agents have'b'een For example, the viscosity of .a toluene solution;

its

of the phenyl ether resin having acid number 251spractically the same asfthat of a solu-' tion of the same resin with-acid number 10. Because of these facts,-it is possible to pro;

.duce these resinous ester complexes with pron nounced uniformity of properties from batch to batch.

The present invention provides new resinous complexes which overcome previous difiiculties to a remarkable degree. It is possible, by the present invention, to produce hard resinous bodies substantially neutral in character, i. e., having acid'numbers of 10 or less, whichare soluble in a common organic solvents, and the solutions of which have comparatively low viscosities. These properties may be obtained without the use of modifying agents and without the hazards generally attendant on the manufacture of synthetic resins of soluble types.

These resinous ester-complexes, because of their inherent properties may be used advantageously as ingredients of protective films or coatings. They are well adapted to replace the natural resin constituents of present-day lacquers. They are much more durable than the natural resins normally used and produce less brittle films. Consequently in a. nitrocellulose lacquer, for example, they may be used in a much higher ratio of resin to nitrocellulose than is possible with the natural resins, and the low viscosit-ies of their solutions greatly facilitates the application of the composite lacquer products. They permit the formulation of lacquers having high solids content, and thereby reduce the number of coats of such alacquer required to obtain the desired build in the dried films. The low acidities of the resins minimize the danger of livering in lacquers containing basic pigments. These resinous ester complexes therefore may not only replace naturally occurring resins advantageously in such compositions but likewise synthetic resins which have been available heretofore.

While particularly adapted to the protective coating field, resin bodies ofthe present invention may be used in other relations; for example, in the preparation of plastic masses, adhesives, or in otherarts requiring fusible soluble types of resins.

I claimi 1. The method of producing resinous bodies which comprises reacting upon esterifiable ethers of glycerol and cyclic bodies with a polybasic carboxylic acid compound.

2. The method of producing resinous bodies which comprises reacting upon esterifiable ethers of glycerol and cyclic bodies with an anhydride of a polyba-sic carboxylic acid.

3. The method of producing resinous bodies which comprises reacting upon esterifiable ethers of glycerol and cyclic bodies with phthalic anhydride.

4. The method of producing resinous bodies which comprises heating an esterifiable ether of lycerol and a cyclic body with a pol'ybasic car oxylic acid compound to effect reaction therebetween and produce a resinous body.

5. The method of producing resinous bodies which comprises heating an esterifiable ether of glycerol and a cyclic body with a polybasic carboxylic acid compound to effect reactions therebetween, and continuing the heating of the reaction mixture, thereby gradually changingthe properties of the resinous body produced.

6. The method of producing resinous bodies which comprises heating an esterifiable ether of glycerol and a cyclic body with a polybasic carboxylic acid compound to effect reaction therebetwcen and produce a resinous body, and continuing the heating of the reaction mixture to reduce the acid number of the resinous body to not over 10.

7 The method of producing resinous bodies which comprises heating an esterifiable ether of glycerol and a cyclic body with phthalic anhydride to effect reaction therebetween and produce a resinous body, and continuing the heating of the reaction mixture, thereby effecting a gradual change in the properties of said resinous body.

8. The method of producing resinous bodies which comprises heating an esterifiable ether of glycerol and a cyclic body with phthalic anhydride to effect reaction therebctween and produce a resinous body, and continuing the heating of the reaction mixture to reduce the acid number thereof to not above 10.

' 9. The method of producingresinousbodies which comprises reacting upon a phenyl ether of glycerol with a polybasic carboxylic acid compound.

10. The method of producing a resinous body which comprises heating a phenyl ether of glycerol with phthalic anhydride.

11. The method of producing a resinous body which comprises heating a phenyl ether of glycerol with phthalic anhydride, thereby forming a resinous condensation product, and continuing the heating to gradually reduce the acid number of said resinous body.

12. The method of producing resinous bodies which comprises heating a tetrahydrofurfuryl ether of glycerol with a polybasic carboxylic acid compound.

13. The method of producing a resinous bod which comprises heating a tetrahydro fur uryl ether of glycerol with phthalic anhydride.

14.'The method of producing a resinous bod which comprises heating tetrahydrofur uryl ether of glycerol with phthalic anhydride, thereby forming a reslnous body, A

and continuing the heating to reduce the acid than 10. 1

15. A resinous condensation product of an esterifiable ether of glycerol and a cyclic body with a polybasic carboxylic acid.

16. A resinous condensation product of an esterifiable etherof glycerol and a cyclic body with a polybasic carboxylic acid, having an acid number of not more than 25.

number of the resinous body to not more 17. A resinous condensationproduct of an.

esterifi'able ether of glycerol and a cyclic body with a polybasic acid, having an acid number not exceeding 10 and which is soluble in lacquer solvent mixtures of esters, alcohols and hydrocarbons and is compatible with nitrocellulose.

18. A resinous condensation product of 

